Olefin polymerization



Patented June l, 1937 ATES LEFIN POLYMERIZATION Robert F. Rutlirui, Whiting, Ind., assignor to Standard Oil Company, Chicago, lll., a corporation of Indiana y Application September 8, 1934, Serial No. 743,251

2 Claims.

This invention relates to a process of converting hydrocarbon gases to higher boiling liquid hydrocarbons principally of the character of gasoline and kerosene. The process employed is 5 known as polymerization, and the gaseous hydrocarbons used as the starting material are usu` ally unsaturated or oleilnic in character. An object of the invention is to eiect the polymerization at moderate temperatures in the presence of catalysts. Another object of the ,invention is to restore the catalyst to its original effectiveness without requiring replacement. Other objects `will become apparent as the-description proceeds.

Piie catalysts employed in this process are of 15, the halogen double salt type of which sodium chloroaluminate is an example. They are compounds of a metal halide of low internal pressure, such as aluminum chloride, ferrie chloride. etc., with other metal halides, usually halldes of high internal pressure such as the alkali metal chlorides, copper chloride, etc. As an example ofA the process, reference will be made to the accompanying drawing which forms a part of this specication.

25 A suitable hydrocarbon gas which may, for

example, contain 2li-30% of propylene in adrnlxture with other hydrocarbons such as ethylene, ethane, butane and propane, is introduced under pressure by line i entering heater 2 where it is 3@ heated to the desired reaction temperature which may be G-800 F. depending on the composition or the gas and the activity of the catalyst, but about 350 F. is satisfactory for the catalysts most commonly used. The heated gas is then led by line 3 to reaction chamber d, preferably entering at a point above the -catalyst bed 5. The pressure may vary over a wide range from 50 to 2000 lbs. per su.4 in., but I nd a pressure of 700 lbs. per sq. in. to be satisfactory.

EAT

o The gases pass through the catalysts leaving the reaction chamber by line S leading to condenser or heat exchanger coil l where higher helling products are condensed and collected-in receiver 3. These are drawn oil' to suitable sta- 45 hilizing and treating apparatus by line Si, while the uncondensed lgases are discharged through line ld. These may be used again in the sys- (Cl. 19d-10) .nace Id provided for the purpose, or furnace may be alternately used for this purpose if de,- sired. The gas may be hydrogen, nitrogen, producer gas, flue gas, methane, or infact any gas l5 which will serve to transfer heat at the temperature desired. As a result of the heating by thev current oi' hot gases, the catalyst is completely freed of sludge contamination, these heavy hydrocarbons being distilled away or decomposed. 20 When the heating is completed, the entire mass of catalyst may be at atemperature of 1800 F. and consists of NaAi'Ch, aluminum oride, sodium chloride, carbon and catalyst support, e. g. coke.' The inert gas stream is discontinued or at least reduced, and a stream of a halogen, such as chlo rine is next introduced into the hot catalyst mass by line l5 and valve i E. The reaction which takes place results in the conversion of the A1203, carbon and NaCl into NaAlCh and carbon monoxide, the latter gas passing out through vent l2; When the entire catalyst has been regenerated in this way, it is allowed to cool to the proper temperature and then the stream of olen gases is resumed. In this way, the catalyst can be used almost indefinitely, and 'oy providing a spare reaction chamber, Athe polymerization can be conl tinued unlnterruptedly by alternately renewing the catalyst in each tower.

After repeated reuse, there is a tendency for i0 the active constituents of the catalyst to be carried away or uxed by the sludge above referred to. This sludge which ows from the catalyst during operation can be drawn oi through lines l2 and i7 and later the valuable constituents re- 45 covered. To replace this loss, I may, from time to time, and before regenerating the catalyst, introduce further quantities of the active catalyst salts through line CS. For example, in tank is, I may have a.- supply of aluminum chloride in 59 solution which is led by line 2t to pump 2i and thence to line i8.A In tank 22 I may likewise have a supply of sodium vchloride in solution, likewise connected to pump 2l by valve 23. 'I'he desired amount of each solution may be admitted to the tower and distributed over the catalyst support therein. 'Ihen when the heated gas from Il is introduced, the water in the solution is completely evaporated, resulting in extensive hydrolysis of AlCla toform A120: which enters the later reaction as described above.

Instead of heating the catalyst mass by means of aheated inert gas as shown, I may employ a catalyst chamber so constructed that heat may i0 be supplied indirectly to the catalyst. This may be done in the conventional way by the use of a heating jacket and :dues disposed'throughout the catalystl bed, a heated fluid being circulated therethrough. The same system of heat exchange may be employed to conduct heat away from the reaction chamber when polymerization' reaction is in progress, as the polymerization reaction is exothermic, requiring removal of heat to maintain the proper temperature. 'Ihe invention has been described by reference to certain catalysts and apparatus but its scope should be limited only by the following claims.

I claim: l 1. In an operation wherein normally gaseous hydrocarbons which are oleilnic in character are subjected to elevated temperatures and pressures yto eifect polymerization thereof into higher boiling liquid hydrocarbons while in contact with a catalyst comprising a double salt of sodium chlorideand aluminum chloride disposed on a suitable support, which operation when carried4 out over a period of time contaminates said catalyst and materially decreases the activity thereof, the improvement of restoring the activity of the catalyst which comprises interrupting the supply of said normally` gaseous hydrocarbons being treated, treating said catalyst with a solution of said double salt to substantially eliminate said contamination and eilect reimpregnation yof said catalyst support with said double salt, heating said catalyst mass to remove moisture therefrom, and thereafter introducing chlorine into intimate contact with said catalyst to restore the activity thereof.

,2. In an operation wherein normally gaseous hydrocarbons which are oleflnic in character are subjected to elevated temperatures and pressures to effect polymerization thereof into higher boiling -liquid hydrocarbons while in contact with a catalyst comprising a double salt of sodiumv .said contamination and eilect reimpregnatlon of said catalyst support with said double sa1t,intro ducing an inert gas, at a temperature higher than the temperature attained during the polymerization of the hydrocarbons, into intimate contact with said catalyst to heat said catalyst and remove moisture therefrom, and thereafter introducing chlorine into intimate contact with said catalyst to restore the activity thereof.

ROBERT E. RUnmUFr 

